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1.
Different polymers containing sulfonic groups attached to the phenyl rings were prepared by sulfonation of polystyrene (PS) and styrene‐block‐(ethylene‐co‐1‐butene)‐block‐styrene (SEBS). The sulfonation degree (SD) was varied between 1 and 20 mol% of the styrene units. Polyphase materials containing sulfonated units were prepared by blending styrene‐block‐butadiene‐block‐styrene (SBS), with both sulfonated PS and sulfonated SEBS in a Brabender mixer. Such a procedure was performed as an alternative route to direct sulfonation of SBS which is actually not selective towards benzene rings because of the great reactivity of the double bonds in polybutadiene (PB) blocks to sulfonation agents. Thermal and dynamic‐mechanic analysis, together with morphology characterization of the blends, is consistent with obtaining partially compatible blends characterized by higher Tg of the polystyrene domains and improved thermal stability. © 2001 Society of Chemical Industry  相似文献   

2.
Effects of a maleated triblock copolymer of styrene–(ethylene‐co‐butene)–styrene (SEBS‐g‐MA) on compatibilization and mechanical properties of nylon‐12,12/nylon‐6 blends were investigated. The results showed that addition of SEBS‐g‐MA could improve the compatibility between nylon‐12,12 and nylon‐6. Nylon‐12,12 could disperse very well in nylon‐6 matrix, although the dispersion of nylon‐6 was poor when nylon‐6 was the dispersed phase. At a fixed nylon‐12,12/nylon‐6 ratio of 30/70, supertoughness was achieved with addition of 15% SEBS‐g‐MA in weight. Scanning electron microscopy of the impact‐fractured surface indicated that cavitation and matrix shear yielding were the predominant mechanisms of impact energy dissipation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1446–1453, 2004  相似文献   

3.
The conditions for the sulfonation of a highly unsaturated styrene–butadiene–styrene triblock copolymer (SBS) in cyclohexane containing a small amount of acetone with acetyl sulfate made by sulfuric acid and acetic anhydride without gelation were studied. After neutralization with metallic ions, the ionomers were characterized with IR spectrophotometry, dynamic mechanical analysis, and transmission electron microscopy. The melt flow, solution properties, and mechanical properties of the ionomers were studied. The results showed that gelation occurred during the sulfonation of SBS in cyclohexane at a 5–10% concentration without acetone, whereas in the presence of 5–10 vol % acetone, sulfonation proceeded smoothly without gelation. Transmission electron microphotographs of the lead ionomer indicated the presence of ionic domains. A dynamic mechanical spectrum showed the presence of three transition temperatures: ?82.9, 68, and 96.5°C. The melt viscosity of the ionomer increased with the sulfonate content. The melt viscosity of the different ionomers neutralized with different cations seemed to decrease with decreasing ionic potential for both monovalent cations and divalent cations The solution viscosity of the sodium‐sulfonated ionomer increased with increasing sulfonate content. The ionomer still behaved as a thermoplastic elastomer and showed better mechanical properties than the original SBS. The tensile strength of the different ionomers decreased as follows. For the monovalent cations, it decreased with decreasing ionic potentials: Li+ > Na+ > K+. For the divalent cations, it decreased with increasing ionic potentials: Pb2+ > Zn2+ > Mg2+. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1398–1404, 2005  相似文献   

4.
Sulfonation of highly stereoregular syndiotactic polystyrene has been accomplished in 1,1,2‐trichloroethane and chloroform (60/40 v/v) mixed solvent. FTIR spectroscopy was used to confirm that the sulfonated syndiotactic polystyrene was the product of the sulfonation reactions. Sodium, potassium, zinc (II), manganese (II) and cobalt (II) salts of the sulfonated polymers exhibited behaviour indicative of strong interactions. FTIR spectroscopy and DSC data showed that the roles of the cation–anionic site interactions in alkali form and transition metal form ionomers are somewhat different. The DSC data also showed that the alkali metal cations had more pronounced effect on Tg than did the transition metal cations. In addition, the crystallization behaviour of the ionomers with a low degree of sulfonation also exhibited considerable differences in comparison with the neat syndiotactic polystyrene. The melting points (Tm) and the degree of crystallization (Xc) were significantly lowered by the presence of the sulfonic acid groups or the sulfonate metal groups. Moreover, the ionomers were more thermally stable and more hygroscopic than the unmodified polymer. © 2001 Society of Chemical Industry  相似文献   

5.
Some properties of styrene‐based ionomers containing alkali metal salts of acrylic acid or methacrylic acid have been investigated. A study has been conducted to examine the influence of the acidic content and nature (acrylic or methacrylic) and the nature of the alkali metal salt on the glass transition temperature, density, melt index and activation energy of a flow of the styrene‐based ionomers. The present studies have indicated that the temperature of glass transition (Tg) of sodium ionomers increases as the sodium content rises and the region of the glass transition broadens. The Tg's of the styrene‐acrylic acid (S‐AA) ionomers do not depend on the nature of the alkali metal introduced into the copolymer. The density of films rises with the content of acid or salt introduced to the polystyrene chain. The melt index of the investigated ionomers depends on the amount and type of the introduced acid and salt as well as on the molecular weight of the initial copolymer. The energy of activation of the flow is independent of the polymer molecular weight; however, the energy of activation of flow of the ionomers increases with larger ionic radii of the introduced alkali metal. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 55–62, 2003  相似文献   

6.
The composites of polyaniline (PAn) and zinc sulfonated ethylene–propylene–diene rubber (EPDM) ionomer were made by polymerization of aniline in the presence of the ionomer by using a direct, one‐step in situ emulsion polymerization technique. The ionomers were prepared by sulfonation of EPDM rubber with acetyl sulfate in petroleum ether, followed by neutralization with zinc acetate solution. The ionomers with sulfonate contents of 10, 24, and 42 mmol SO3H/100 g were used for preparation of PAn/ionomer composites. The in situ polymerization of aniline was carried out in an emulsion comprising water and xylene containing the ionomer in the presence of dodecyl benzene sulfonic acid, acting as both a surfactant and a dopant for PAn. The composite was characterized by IR and WAXD. The composite obtained can be processed by melt method. The conductivity of the composite with lower sulfonate content was higher than that with higher sulfonate content. Conductivity of the composites exhibits a percolation threshold at about 13 wt % PAn. When the sulfonated content is 10 or 24 mmol SO3H/100 g and PAn content is 4–10 wt %, the composites behave as a thermoplastic elastomers with high ultimate elongation and low permanent set. The conductivity of the composite after secondary doping with m‐cresol is higher than the composite before secondary doping by about one order. Addition of zinc stearate as an ionic plasticizer lowers both the conductivity and the mechanical strength of the composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2211–2217, 2004  相似文献   

7.
A series of well-characterized telechelic polyisobutylene-based sulfonated metal-neutralized ionomers have been studied using thermal-mechanical analysis (TMA). These ionomers serve as models in the sense that the ionic groups are located exclusively at the chain ends and hence the ionomeric character is well defined. The chemical parameters varied are (i) molecular weight, (ii) molecular architecture (linear or triarm products), (iii) addition of excess neutralizing agent, and (iv) type of cation. The effect of the above parameters on the glass transition temperature and the softening temperature (after the rubbery plateau region) is presented. It is observed that the glass transition temperature is only slightly affected by the above parameters due to the very low ionic content in these ionomers (< 2 mol %). In the case of the triarm ionomer with excess neutralizing agent, the softening temperature following the rubbery plateau is much higher than that of the linear difunctional species. Linear monofunctional species do not show a rubbery plateau behavior and readily flow above their Tg in the absence or presence of excess neutralizing agent. The excess salt is most likely located at the ionic sites rather than being uniformly distributed throughout the matrix. Zinc-neutralized ionomers were found to have the lowest softening temperatures as compared to the corresponding calcium and potassium-neutralized ionomers. The covalent character of zinc is believed to be primarily responsible for this behavior. Thermal stability of these metalneutralized ionomers is not significantly different from the sulfonated hydrocarbon precursor polymer. However, the unneutralized acid precursor polymers start to discolor at relatively lower temperatures, thereby suggesting poorer thermal stability.  相似文献   

8.
The influence of sulfonation reaction time, temperature and the parent polystyrene (PS) particle size on the degree of sulfonation (DS), ion exchange capacity (IEC), morphology and glass transition temperature (Tg) of sulfonated polystyrene (SPS) particles was investigated. A longer reaction time (ca 2 h) at 40 °C and a smaller particle size resulted in SPS particles with a high DS. It was found that a larger PS particle size did not readily yield SPS particles with a high DS even with a longer reaction time. Contrary to the popular belief in the literature that a higher DS ensures a high IEC, we observed that the proportionality of IEC to DS is primarily controlled by the SPS particle size. Larger IEC values were obtained for larger particles rather than smaller ones despite their similar DS, owing to the presence of strong interactions between ? SO3H groups within the particles in the latter case which restricts the availability of free H+ for ion exchange. The SPS particles displayed a core‐shell morphology in which the outer shell appeared because of sulfonation on the PS. The DS value and the SPS particle size significantly influenced the shell thickness and thereby the morphology of the SPS particles. Copyright © 2012 Society of Chemical Industry  相似文献   

9.
The effect of poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) copolymer on the thermal and dielectric properties of polypropylene (PP)—nanosilica (NS) composites in relation with morphological aspects revealed by atomic force microscopy (AFM) was investigated in this article. SEBS hindered the crystallization process of PP in PP/NS composites, leading to a smaller degree of crystallinity and lower perfection of crystalline structure. Broader lamellar thickness distribution was obtained in nanocomposites containing SEBS. Almost two times higher dielectric loss as compared to PP reference and two relaxation processes were detected in εr ′′(f) curves of nanocomposites. The first peak, in the same frequency domain as for the references, was assigned to α‐relaxation of polymer components together with interfacial polarization. The relaxation time follows the Arrhenius law with an activation energy of 80–90 kJ/mol. For the second process, the temperature dependence of the relaxation times obeyed the VFT equation. The dielectric changes following the incorporation of SEBS support its tendency to hinder the motional processes in PP, in accordance with DSC results. A smooth transition from a phase rich in SEBS to one containing mainly PP was detected in the AFM image of the composite with the larger amount of SEBS, emphasizing the good compatibility at the PP/SEBS interface. POLYM. ENG. SCI., 53:2081–2092, 2013. © 2013 Society of Plastics Engineers  相似文献   

10.
Poly(2,6‐dimethyl‐1,4‐phenylene oxide)/polyamide 6 (PPO/PA6 30/70) blends were impact modified by addition of three kinds of maleated polystyrene‐based copolymers, i.e., maleated styrene‐ethylene‐butylene‐styrene copolymer (SEBS‐g‐MA), maleated methyl methacrylate‐butadiene‐styrene copolymer (MBS‐g‐MA), and maleated acrylonitrile‐butadiene‐styrene copolymer (ABS‐g‐MA). The mechanical properties, morphology and rheological behavior of the impact modified PPO/PA6 blends were investigated. The selective location of the maleated copolymers in one phase or at interface accounted for the different toughening effects of the maleated copolymer, which is closely related to their molecular structure and composition. SEBS‐g‐MA was uniformly dispersed in PPO phase and greatly toughened PPO/PA6 blends even at low temperature. MBS‐g‐MA particles were mainly dispersed in the PA6 phase and around the PPO phase, resulting in a significant enhancement of the notched Izod impact strength of PPO/PA6 blends from 45 J/m to 281 J/m at the MBS‐g‐MA content of 20 phr. In comparison, the ABS‐g‐MA was mainly dispersed in PA6 phase without much influencing the original mechanical properties of the PPO/PA6 blend. The different molecule structure and selective location of the maleated copolymers in the blends were reflected by the change of rheological behavior as well. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

11.
The copolymer of styrene–ethylene–butylene–styrene triblock copolymer‐g‐polylactic acid (SEBS‐g‐PLA) was successfully prepared using a novel solvothermal synthetic method, in which the graft copolymerization of PLA and SEBS was simply performed in cholorform solution at 100–150°C with benzoyl peroxide (BPO) as initiator. The effect of various factors including the reaction temperature and time and the content of BPO and PLA on the graft copolymerization was investigated in detail. It is found that the optimal reaction condition for the grafted copolymers SEBS‐g‐PLA was 120°C for 5 h, while the optimal formulation of SEBS/PLA/BPO was 5 g/2 g/0.5 g in 30 mL chloroform. The properties and microstructures of the obtained SEBS‐g‐PLA copolymers were also studied. The tensile strength and elongation at break were higher than that of pure SEBS and improved with the increase of grafting degree. In addition, SEBS‐g‐PLA copolymer possessed two‐phase structure with vague phase boundaries. The as‐prepared SEBS‐g‐PLA copolymers can be used as the toughening component to improve the impact strength of PLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

12.
Polystyrene (PS)/polyamide 1212 (PA 1212) blends were compatibilized with a maleated triblock copolymer of styrene–(ethylene‐co‐butene)–styrene (SEBS‐g‐MA). Scanning electron microscopy revealed that the addition of SEBS‐g‐MA was beneficial to the dispersion of PA 1212 in the PS matrix because of the reaction between them. The variation of the fraction of SEBS‐g‐MA in the blends allowed the manipulation of the phase structure, which first formed a sheetlike structure and then formed a cocontinuous phase containing PA 1212/SEBS‐g‐MA core–shell morphologies. As a result, the mechanical properties, especially the Charpy notched impact resistance, were significantly improved with the addition of SEBS‐g‐MA. Differential scanning calorimetry (DSC) data indicated that the strong interaction between SEBS‐g‐MA and PA 1212 in the blends retarded the crystallization of PA 1212. The heat distortion temperature of the compatibilized blends was improved in comparison with that of the unmodified blend, probably because of the apparent increase in the glass‐transition temperature with an increasing concentration of SEBS‐g‐MA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1354–1360, 2005  相似文献   

13.
Linear and three-arm star poly(styrene-b-isobutylene-b-styrene) (PS-PIB-PS) block copolymer ionomers possessing various counterions and levels of sulfonation were synthesized by sulfonating the polystyrene blocks of PS-PIB-PS block copolymers. Analysis of compression-molded films of the ionomers showed that the incorporation of sulfonate groups into the polystyrene blocks of these materials resulted in an increase in tensile strength, a decrease in elongation at break, and a persistence of elastic properties to much higher temperatures as compared with unsulfonated precursors. Among all counterions studied, zinc resulted in the strongest ionomers and potassium yielded the most easily processed ionomers. Dynamic mechanical analysis showed that the block copolymer ionomers possessed a phase-separated morphology; however, anomalous relaxations observed during the first heating cycle, but that were substantially reduced or completely absent in subsequent cycles, implied that strong ionic interactions were causing reduced processability and the formation of nonequilibrium morphologies. The observed relaxations were interpreted to be domain rearrangements brought about by the thermal energy supplied by the dynamic experiment. Annealing of films of relatively low ionic contents yielded viscoelastic behavior that was consistent with an equilibrium morphology characterized by phase-separated, partially sulfonated polystyrene domains of the same density and size as the polystyrene domains of the unsulfonated precursor. Compression molded films of high ionic content yielded a higher rubbery plateau modulus than the unsulfonated precursor, suggesting a different morphology. Solution-cast films of zinc ionomers exhibited two values for the rubbery modulus, a higher values at temperature below the Tg of polystyrene and a lower value at temperature above the Tg of polystyrene. Thermogravimetric analysis revealed the major mass-loss process of the parent, linear block copolymer at 417°C (mid-point) and of the tetramethyl ammonium ionomer at 431°C.  相似文献   

14.
In this study, the mechanical and chemical properties of a series of sulfonated poly(styrene‐isobutylene‐styrene) (SIBS) block copolymers were evaluated using a combination of nanoindentation, dynamic mechanical analysis (DMA), elemental analysis (EA), Fourier transform infrared spectroscopy (FTIR), water absorption, and small angle X‐ray scattering studies (SAXS). The materials properties were characterized as a function of the sulfonation percent in the block copolymers, as well as a result of the counter‐ion substitution with Mg2+, Ca2+, and Ba2+. Nanoindentation studies revealed that the elastic modulus (E) and hardness (H) increase with sulfonation up to a certain level, at which point, the effect of water content further hinders any mechanical reinforcement. The incorporation of counter‐ions increases E and H, but the results are dependent upon the size of the counter‐ion. DMA results showed that the polymer maintained the glass transition temperature (Tg) of the polyisobutylene (PIB) segment (?60°C) regardless of the sulfonation level or counter‐ion substituted. However, both the shoulder of the PIB Tg (?30°C), which was probably caused by a Rouse‐type motion, as well as the Tg of polystyrene (105°C) disappeared upon sulfonation. Counter‐ion substitution increased the storage modulus of the rubbery plateau, which is indicative of a stronger and more thermally stable crosslinked complex formation. Additional unique relaxations were observed with the counter‐ions, and could be attributed to the stretching/rotation of the S? O bond and the interaction of the cations with the oxygen in the sulfonic group. FTIR results also revealed a unique shifting of the asymmetric S? O band when counter‐ions were added. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40344.  相似文献   

15.
The preparation and physical properties of some ionomers have been investigated. The addition of CH3I significantly improved the conductivity of the ionomers. At room temperature, the highest ionic conductivity value was found to be 4.93 10−8 S cm−1 in the I4 ionomer. The conductivity data do not obey the Arrhenius law and the non‐linearity indicates ionic transport. The alternating current conductivity parameters and dielectric constants of the ionomers were determined. Copyright © 2005 Society of Chemical Industry  相似文献   

16.
Nafion®‐117, sulfonated polysulfone (sPSF) and sulfonated polyetherketone (sPEK) are characterized using broadband dielectric spectroscopy in the frequency range of 10 MHz–100 mHz. Overall, there are 4–5 relaxation processes in these sulfonated membranes and a comparison of their spectral features allows assigning the relaxation processes. At an optimum amplitude of ~100 mVrms, all the relaxations are clearly defined as the electrode polarization is minimized. At low temperatures (?130 °C), these membranes show a broad relaxation peak in the mid‐frequency region, which quickly shifts towards the high‐frequency region as the temperature is increased to ?90 °C. This peak is observed in proton exchange membranes for the first time due to the use of low ac amplitude, and it is assigned to the relaxation of the confined water in the micro‐pores. With all the membranes, the peak associated with ? SO3H group relaxation is observed in the same frequency range at a temperature of ~?80 °C. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44790.  相似文献   

17.
Poly[bis(3‐methylphenoxy)phosphazene] was sulfonated in a solution with SO3 and solution‐cast into 100–200‐μm‐thick membranes from N,N‐dimethylacetamide. The degree of polymer sulfonation was easily controlled and water‐insoluble membranes were fabricated with an ion‐exchange capacity (IEC) as high as 2.1 mmol/g. For water‐insoluble polymers, there was no evidence of polyphosphazene degradation during sulfonation. The glass transition temperature varied from −28°C for the base polymer to −10°C for a sulfonated polymer with an IEC of 2.1 mmol/g. The equilibrium water swelling of membranes at 25°C increased from near zero for a 0.04‐mmol/g IEC membrane to 900 % when the IEC was 2.1 mmol/g. When the IEC was < 1.0 mmol/g, SO3 attacked the methylphenoxy side chains at the para position, whereas sulfonation occurred at all available aromatic carbons for higher ion‐exchange capacities. Differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized microscopy showed that the base polymer, poly[bis(3‐methylphenoxy)phosphazene], was semicrystalline. For sulfonated polymers with a measurable IEC, the 3‐dimensional crystal structure vanished but a 2‐dimensional ordered phase was retained. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 387–399, 1999  相似文献   

18.
This investigation examines characteristics of sulfonated polyether imides (SPEI) with various ion exchange capacity values (IEC) and completes previous work to enable its blends to be adopted as polyelectrolyte in direct methanol fuel cells (DMFC). Polyether imides (PEI) were sulfonated by using chlorosulfonic acid as the sulfonating agent and chloroform as the solvent. The structure of SPEI was observed by FTIR and 1H NMR. The sulfonate or sulfonic acid content of the polymers, expressed as a number per repeat unit of the polymer, was accurately determined by elemental analysis and conductometric titration. Physical properties such as solubility, intrinsic viscosities, thermal stability, and glass transition temperature (Tg) were studied for both PEI and SPEI. TGA‐FTIR verified that sulfonic groups, attached to the aromatic ring in the PEI backbone, are split at 230–350°C, but the main‐chain splitting temperature of SPEI is similar to that of pure polymer. The sulfonated samples exhibited good solubilities and increased glass transition temperatures (Tg values) as degree of sulfonation (DS) increased; two Tg values were detected when IEC was sufficiently high. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

19.
A new, milder sulfonation process was used to produce ion‐exchange polymers from a commercial polysulfone (PSU). Membranes obtained from the sulfonated polysulfone are potential substitutes for perfluorosulfonic acid membranes used now in polymer electrolyte fuel cells. Sulfonation levels from 20 to 50% were easily achieved by varying the content of the sulfonating agent and the reaction time. Ion‐exchange capacities from 0.5 to 1.2 mmol SO3H/g polymer were found via elemental analysis and titration. Proton conductivities between 10−6 and 10−2 S cm−1 were measured at room temperature. An increase in intrinsic viscosity with increasing sulfonation degree confirms that the sulfonation process helps to preserve the polymer chain from degradation. Thermal analysis of the sulfonated polysulfone (SPSU) samples reveals higher glass transition temperatures and lower decomposition temperatures with respect to the unsulfonated sample (PSU). Amorphous structures for both PSU and SPSU membranes were detected by X‐ray diffraction analysis and differential scanning calorimetry. Preliminary tests in fuel cells have shown encouraging results in terms of cell performance. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1250–1257, 2000  相似文献   

20.
Ionomers were prepared by partially sulfonating the styrene units of a poly(ethylene‐ran‐styrene) (ES) copolymer. The metal salt derivatives of sulfonated ES had higher Tg, melt viscosity and rubbery modulus than did the parent ES because of the formation of labile, physical crosslinks from intermolecular dipole–dipole associations between metal sulfonate groups. Microphase separation of ion‐rich aggregates with a characteristic size of 3–9 nm also occurred as a result of the strong intermolecular associations. Copyright © 2005 Society of Chemical Industry  相似文献   

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